TWI475073B - Silicone liquid crystal aligning agent and liquid crystal alignment film - Google Patents

Description

Lanthanide liquid crystal alignment agent and liquid crystal alignment film

The present invention relates to a liquid crystal alignment agent comprising a polyoxyalkylene obtained by polycondensing an alkoxysilane, a liquid crystal alignment agent with a specific ethylene glycol compound, and a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display having the liquid crystal alignment film thereof element.

The liquid crystal display element is disposed opposite to two substrates of a liquid crystal alignment film mainly composed of polylysine and/or polyimide, which is provided on a transparent electrode, and is known to be filled with a liquid crystal substance in a gap thereof. structure. The most widely known method is a TN (Twisted Nematic) type liquid crystal display element, but there is a STN (Super Twisted Nematic) type that can achieve a higher contrast, and IPS (In-Plane) with less viewing angle dependence. Switching type, vertical alignment (VA: Vertical Alignment) type, etc. were developed.

Among them, a vertical alignment type liquid crystal display device driven by a thin film transistor (TFT: Thin Film Transistor) has a high response speed, a wide viewing angle, and a high contrast characteristic, and can realize a higher quality MVA (Multi- A new vertical alignment type liquid crystal display element such as domain vertical Alignment), ASV (Advanced Super View), PVA (Patterned Vertical Alignment) or the like is proposed.

The liquid crystal alignment film provided in the liquid crystal display elements of the prior art has a large influence on various characteristics such as electrical characteristics of the liquid crystal display element while aligning the liquid crystal. Therefore, even for such a new vertical alignment type display element, liquid crystal alignment films suitable for such are gradually being developed.

For example, in order to obtain a liquid crystal alignment film having a good vertical alignment property, a method of introducing a long-chain alkyl chain into polyacrylic acid and/or polyimine is proposed (for example, refer to Patent Document 1), and a cyclic substituent is introduced. Method etc. (For example, refer to Patent Document 2.)

Further, in order to achieve a highly stable vertical alignment property, it is necessary to introduce a large amount of a long-chain alkyl group to cause the film to be water-repellent to lower the energy of the surface.

Further, in the case of having a good vertical alignment property and imparting a high voltage holding ratio to the element and/or an electrical property of a low residual DC, a specific cyclic substitution is introduced in the polyperglycine and/or polyimine. The base method was proposed.

(For example, refer to Patent Document 3.)

Recently, in the light source for liquid crystal projectors used for commercial use and home theaters (referred to as a third thin-type television rear projection television), a metal halide lamp having a strong irradiation intensity is used, which is conventionally used. In addition to the liquid crystal alignment film material formed of the organic polymer, it is necessary to use other liquid crystal alignment film materials having high heat resistance and high light resistance. One of the countermeasures is to use an inorganic polymer-based liquid crystal alignment film material for this purpose.

However, research and development of liquid crystal alignment film materials based on inorganic polymers are mainly based on vapor deposition materials (see, for example, Patent Documents 4 and 5), and coating materials which are advantageous for the manufacture of large-screen displays. The report is not available. Therefore, liquid crystal alignment film materials based on inorganic polymers have hitherto been used.

In the report of using a coating-based inorganic polymer as a liquid crystal alignment film material, for example, a liquid crystal alignment agent composition containing a reaction product of a tetraalkoxysilane, a trialkoxysilane, and water and a glycol ether solvent is proposed. . These compositions can only prevent display defects, and have good visual persistence characteristics after long-term driving, so that liquid crystal alignment ability is not lowered, and a liquid crystal alignment film having less reduction in voltage and heat voltage retention can be formed (for example, refer to the patent document) 6, 7.) However, to date, there has not been a liquid crystal alignment film material which is capable of achieving a practical level of coating-based inorganic polymer.

In contrast to this trend, the technological innovation of liquid crystal display elements starting with liquid crystal televisions has been awakened, and in order to achieve this, in particular, improving the reliability of components has become an important issue.

As one of the reliability of the element, the electrical reliability of the element can be exemplified. The reliability, particularly the electrical reliability, of the conventional TFT liquid crystal display device is confirmed by the voltage holding ratio corresponding to the 30 Hz operation of the liquid crystal display element or its temperature characteristics, but such a measurement method is difficult to check. Minor differences cannot solve the above problems.

Therefore, in order to confirm the method of higher reliability, there has been proposed a method of measuring the voltage holding ratio by using a low-cycle driving element by increasing the interval between the applied pulse voltages on the liquid crystal display element. (For example, refer to Patent Document 8.)

As another reliability of the component, reliability in the manufacture of the component can be exemplified. That is, the reliability of the liquid crystal display element is not only a reliability of display characteristics such as a monitor or a television, but also has a direct influence on the improvement of the yield in the manufacturing process, so that it is very important.

Further, in recent years, in the case where the liquid crystal display element is enlarged, the yield in the manufacturing step is more affected than the conventional one in the productivity of the liquid crystal display element. In the flexo printing or the like, the coating property at the time of applying the liquid crystal alignment film not only greatly affects the image quality of the liquid crystal display element, but also causes deterioration in yield.

In particular, in the case of a vertical alignment type display element, it is necessary to vertically align the liquid crystal, and it is necessary to introduce a long-chain alkyl group into the inorganic polymer skeleton. (For example, refer to Patent Documents 6 and 7.)

However, the more the amount of the long-chain alkyl group introduced, the more the coating property is deteriorated. Further, the more the introduction amount of the alkoxysilane having a long-chain alkyl group, the lower the denseness of the film, and the display failure due to the decrease in hardness, and the display short circuit caused by the tunnel current. .

Therefore, in order to solve the above problems, for vertical alignment, coating properties such as printability are excellent, and the demand for a liquid crystal alignment film material based on an inorganic polymer is gradually increasing.

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

An object of the present invention is to provide a fluorene-based liquid crystal alignment agent which is excellent in liquid crystal alignment, can form a high-hardness liquid crystal alignment film, and has excellent coatability such as flexographic printing. Second, a liquid crystal alignment film obtained from a lanthanide liquid crystal alignment agent is provided. Third, a liquid crystal display element having the liquid crystal alignment film is provided.

The inventors of the present invention have finally completed the present invention based on the results of the research in view of the above circumstances.

That is, the present invention has the following gist.

A liquid crystal alignment agent comprising the following polyoxyalkylene (A) and ethylene glycol compound (B), polyoxyalkylene (A): containing an alkoxy group represented by the following formula (1) A polyoxyalkylene obtained by polycondensation of at least one alkoxydecane in a decane, R ¹ _n Si(OR ² ) _4-n (1) (R ¹ represents an organic group having 7 to 30 carbon atoms, and R ² represents a hydrocarbon group having 1 to 5 carbon atoms, n is an integer of 1 to 3) an ethylene glycol compound (B): two carbon atoms having a bonded hydroxyl group and a hydrogen atom, and the two carbon atoms may have a A structure in which an aliphatic group of a hetero atom is bonded, and a continuous ethylene glycol compound having 3 to 6 carbon atoms.

2. The liquid crystal alignment agent of claim 1, which further comprises the following solvent (C), the solvent (C): a solvent having a hydroxyl group, which is different from the one defined in the first item of the patent application scope A solvent of a compound of the structure of the diol compound (B).

3. The liquid crystal alignment agent according to Item 1 or 2, wherein the polyoxyalkylene (A) contains an alkoxydecane of the formula (1) in an amount of 0.1 to 30 mol% of an alkoxysilane. The polyoxyalkylene obtained by polycondensation of oxydecane.

4. The liquid crystal alignment agent according to any one of the items 1 to 3, wherein the polyoxyalkylene (A) is used in combination with at least one of the alkoxydecane represented by the formula (1) and at least one The polyoxane obtained by polycondensation of the alkoxydecane of the alkoxydecane represented by the formula (2) above, R ³ _m Si(OR ⁴ ) _4-m (2)

(R ³ represents a hydrogen atom, a halogen atom or an organic group having 1 to 6 carbon atoms, R ⁴ represents a hydrocarbon group having 1 to 5 carbon atoms, and m represents an integer of 0 to 3).

5. The liquid crystal alignment agent according to any one of items 1 to 4, wherein the ethylene glycol compound (B) is selected from the group consisting of 1,3-propanediol, 1,3-butanediol, and 1,4- Butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,6-hexanediol, At least one of a group consisting of diethylene glycol and dipropylene glycol.

6. The liquid crystal alignment agent according to any one of items 1 to 5, wherein the content of the polyoxyalkylene (A) in the liquid crystal alignment agent is a total alkoxy group used for obtaining the polyoxyalkylene (A). The argon atom of decane is converted to SiO ₂ in a conversion ratio of SiO ₂ of 0.5 to 20% by mass.

7. The liquid crystal alignment agent according to any one of items 1 to 6, wherein the content of the ethylene glycol compound (B) in the liquid crystal alignment agent is relative to the total alkane to be used for obtaining the polyoxyalkylene oxide (A). The argon atom of oxydecane is 2.5 to 19,800 parts by mass in terms of 100 parts by mass in total of SiO ₂ .

A liquid crystal alignment film obtained by using the liquid crystal alignment agent according to any one of items 1 to 7.

A liquid crystal display device comprising the liquid crystal alignment film of the eighth aspect.

When the fluorene-based liquid crystal alignment agent of the present invention contains a specific ethylene glycol compound, it is easy to improve the water repellency of the film at the time of film formation as compared with the case where the liquid crystal alignment agent is not used, and the result is high compactness. A liquid crystal alignment film having high hardness and good liquid crystal alignment property of the film and excellent coatability. Therefore, it is possible to provide a liquid crystal display element with high reliability and high image quality.

Best form for implementing the invention

The details of the invention are as follows.

<Polyoxane A> The polyoxyalkylene (A) used in the present invention is obtained by polycondensation of an alkoxysilane having an alkoxysilane represented by the following formula (1) as an essential component.

R ¹ _n Si(OR ² ) _4-n (1)

(R ¹ is an organic group having 7 to 30 carbon atoms, R ² is a hydrocarbon group having 1 to 5 carbon atoms, and n is an integer of 1 to 3.)

R ¹ in the formula (1) (hereinafter also referred to as the first organic group), preferably 8 to 20, particularly preferably 8 to 18, and the polyoxyalkylene (A) has the first organic group The effect of aligning the liquid crystal in one direction.

Examples of the above first organic group include an alkyl group, a perfluoroalkyl group, an alkenyl group, an allyloxyalkyl group, a phenethyl group, a perfluorophenylalkyl group, a phenylaminoalkyl group, and a benzene group. Vinylalkyl, naphthyl, benzoyloxyalkyl, alkoxyphenoxyalkyl, cycloalkylaminoalkyl, epoxycycloalkyl, N-(aminoalkyl)aminoalkane , N-(aminoalkyl)aminoalkylphenethyl, bromoalkyl, diphenylphosphino, N-(methacryloxyhydroxyalkyl)aminoalkyl, N-(propylene Alkoxy hydroxyalkyl)aminoalkyl, substitutable and having at least one nail a one-valent organic group of a ring, a substituted organic group having at least one steroid skeleton, or a substituent selected from the group consisting of a fluorine atom, a trifluoromethyl group, and a trifluoromethoxy group, and having 7 carbon atoms The above one-valent organic group or a photosensitive group such as a cinnamyl group or a chalcone group. Among these, an alkyl group and a perfluoroalkyl group are preferred because they are easy to obtain. The polyoxyalkylene (A) used in the present invention may have a plurality of such first organic groups.

When the first organic group is 100 moles per mole of the ruthenium atom having the polyoxyalkylene (A), if it is less than 0.1 mole, since it is not able to obtain good liquid crystal alignment, it is preferably 0.1 mol or more, more preferably More than 0.5 moles, especially preferably more than 1 mole. On the other hand, when it exceeds 30 m, the formed liquid crystal alignment film is not sufficiently cured, and therefore it is preferably 30 mol or less, more preferably 22 m or less, and particularly preferably 15 m or less.

In other words, when the total alkoxy decane used for obtaining the polyoxyalkylene oxide (A) is less than 0.1 mol%, good liquid crystal alignment property cannot be obtained, so it is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, particularly preferably 1 mol or more. Moreover, when it exceeds 30 mol%, since the formed liquid crystal alignment film cannot be sufficiently hardened, it is preferably 30 mol% or less, more preferably 22 mol% or less, and particularly preferably 15 mol% or less.

Specific examples of the alkoxydecane represented by the formula (1) are exemplified here, but are not limited thereto.

Heptyltrimethoxydecane, heptyltriethoxydecane, octyltrimethoxydecane, octyltriethoxydecane,decyltrimethoxydecane,decyltriethoxydecane,12 Trimethoxy decane, dodecyl triethoxy decane, hexadecyl trimethoxy decane, hexadecyl triethoxy decane, heptadecyl trimethoxy decane, heptadecyl triethoxy decane, ten Octamethoxy decane, octadecyltriethoxy decane, ninyltrimethoxydecane, nineteen-triethoxydecane, undecyltriethoxydecane, undecyltrimethoxydecane, 21-Tetradecyltriethoxydecane, allyloxyundecyltriethoxydecane, tridecafluorooctyltrimethoxydecane, tridecafluorooctyltriethoxydecane, isooctyl Triethoxydecane, phenethyltriethoxydecane, pentafluorophenylpropyltrimethoxydecane, N-phenylaminopropyltrimethoxydecane, N-(triethoxydecylpropyl) Tertiary decylamine, styrylethyltriethoxydecane, (R)-N-1-phenylethyl-N'-triethoxydecylpropylurea, (1-naphthyl)tri Ethoxygen Baseline, (1-naphthyl)trimethoxydecane, m-styrylethyltrimethoxydecane, p-styrylethyltrimethoxydecane, N-[3-(triethoxydecyl)propyl Lysine, 1-trimethoxydecyl 2-(p-aminomethyl)phenylethane, 1-trimethoxydecyl 2-(m-aminomethyl)phenylethane, benzene Mercaptooxypropyltrimethoxydecane, 3-(4-methoxyphenoxy)propyltrimethoxydecane, N-triethoxydecylpropyl quinuclidinic acid ethyl ester, 3-(N -cyclohexylamino)propyltrimethoxydecane, 1-[(2-triethoxydecyl)ethyl]cyclohexane-3,4-epoxide, N-(6-aminohexyl) Aminopropyltrimethoxydecane, aminoethylaminoaminomethylphenethyltrimethoxydecane, 11-bromoundosyltrimethoxydecane, 2-(diphenylphosphino)ethyltriethoxy Baseline, N-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxydecane, N-(3-propenyloxy-2-hydroxypropyl) 3-amino-propyltriethoxydecane, and the like. With respect to the alkoxydecane represented by the formula (1), dodecyltriethoxydecane, octadecyltriethoxydecane, octyltriethoxydecane, tridecafluorooctyltriethoxydecane Preferably, dodecyltrimethoxydecane, octadecyltrimethoxydecane, or octyltrimethoxydecane is preferred.

In the present invention, a plurality of kinds of alkoxydecanes represented by the formula (1) may be used in combination.

Further, in the present invention, an alkoxydecane other than the alkoxydecane represented by the formula (1) may be used in combination. In particular, in order to improve the adhesion to the substrate and the affinity with the liquid crystal molecules, a group different from the first organic group may be used in combination with the effect of the present invention (hereinafter also referred to as the first 2 an organic alkoxy decane.

The second organic group is an organic group having 1 to 6 carbon atoms. Examples of the second organic group may contain an aliphatic hydrocarbon; a ring structure such as an aliphatic ring, an aromatic ring or a heterocyclic ring; an unsaturated bond; a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom, etc., may have a branch Chain structure, an organic group having 1 to 3 carbon atoms. Further, the second organic group may contain a halogen atom, a vinyl group, an amine group, a glycidyl group, a thiol group, a ureido group, a methacryloxy group, an isocyanate group, an acryloxy group or the like.

The polyoxyalkylene (A) used in the present invention may have one or a plurality of kinds of the second organic groups.

The alkoxy decane represented by the following formula (2) is exemplified as the alkoxy decane having the above-mentioned second organic group.

R ³ _m Si(OR ⁴ ) _4-m (2)

(R ³ represents a hydrogen atom, a halogen atom or an organic group having 1 to 6 carbon atoms, R ⁴ represents a hydrocarbon group having 1 to 5 carbon atoms, and m represents an integer of 0 to 3.)

In the alkoxydecane of the formula (2), the alkoxydecane wherein m is 0 represents a tetraalkoxydecane. The tetraalkoxydecane is preferred because it is easily condensed with the alkoxydecane represented by the formula (1) to obtain a polyoxyalkylene (A). Specific examples of the alkoxy decane in which m is 0 in the formula (2) include tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetrabutoxy decane, and the like. Oxydecane and tetraethoxydecane are preferred.

Further, when the organic group having 1 to 6 carbon atoms of R ³ in the formula (2) represents the same group as the second organic group. Therefore, in these cases, the example of R ^{3 is} the same as that described for the second organic group.

The alkoxy decane having 1 to 6 carbon atoms of R ³ represented by the formula (2) may, for example, be exemplified below.

When m=1, methyltrimethoxydecane, methyltriethoxydecane, propyltrimethoxydecane, propyltriethoxydecane, methyltripropoxydecane, or 3-amino group may, for example, be mentioned. Propyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-2(aminoethyl)3-aminopropyltriethoxydecane, N-2(aminoethyl)3 -Aminopropyltrimethoxydecane, 3-(2-aminoethylaminopropyl)trimethoxydecane, 3-(2-aminoethylaminopropyl)triethoxydecane, 2 -Aminoethylaminomethyltrimethoxydecane, 2-(2-aminoethylthioethyl)triethoxydecane, 3-hydrothiopropyltriethoxydecane, 3-hydrogen Thiomethyltrimethoxydecane, 3-ureidopropyltriethoxydecane, 3-ureidopropyltrimethoxydecane, ethylenetriethoxydecane, ethylenetrimethoxydecane, allyltriethoxy Decane, 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-propene oxime Oxypropyl triethoxy decane, 3-isocyanate Triethoxy decane, trifluoropropyltrimethoxydecane, chloropropyltriethoxydecane, bromopropyltriethoxydecane, 3-hydrothiopropyltrimethoxydecane, phenyltriethyl Oxydecane, phenyltrimethoxydecane, and the like.

Further, when m=2, dimethyldiethoxydecane, dimethyldimethoxydecane, diphenyldiethoxydecane, diphenyldimethoxydecane, and methyldiethyl can be exemplified. Oxy decane, methyl dimethoxy decane, methyl phenyl diethoxy decane, methyl phenyl dimethoxy decane, 3-aminopropyl methyl diethoxy decane, 3-amino group Propylmethyldimethoxydecane, 3-ureidomethyldiethoxydecane, 3-ureidomethyldimethoxydecane, and the like.

Further, when m=3, trimethylethoxy decane, trimethyl methoxy decane, dimethylphenyl ethoxy decane, dimethyl phenyl methoxy decane, and 3-amino group may, for example, be mentioned. Propyl dimethyl ethoxy decane, 3-aminopropyl dimethyl methoxy decane, 3-ureido dimethyl ethoxy decane, 3-aminopropyl dimethyl methoxy decane Wait.

In the alkoxy decane of the formula (2), specific examples of the alkoxy decane in the case where R ³ is a hydrogen atom or a halogen atom may, for example, be trimethoxydecane, triethoxydecane or tripropoxydecane. Tributoxy decane, chlorotrimethoxy decane, chlorotriethoxy decane, and the like.

When the alkoxy decane represented by the above formula (2) is used, one type or plural types may be used as needed.

When the alkoxydecane represented by the formula (2) is used in combination, the alkoxydecane represented by the formula (2) is 99.9 mol% or less in the total alkoxydecane used to obtain the polyaluminoxane (A). Preferably, it is preferably 99.5 % by mole or less, and particularly preferably 99 % by mole. Further, the alkoxydecane represented by the formula (2) is preferably 70 mol% or more, more preferably 78 mol% or more, and particularly preferably 85 mol% or more.

The polyoxyalkylene (A) used in the present invention is obtained by condensing an alkoxydecane having alkoxysilane represented by the above formula (1) as a preferred component in an organic solvent. In this case, an alkoxysilane having an alkoxydecane represented by the formulae (1) and (2) is preferred. Usually, the polyoxyalkylene (A) is obtained by polycondensing such an alkoxysilane, uniformly dissolving in an organic solvent, and forming a solution.

The method for condensing the polyoxyalkylene (A) used in the present invention is not particularly limited, and an alkoxydecane may be exemplified by hydrolysis in an alcohol or an ethylene glycol solvent. The method of condensation. At this point, hydrolysis. The condensation reaction can be partial or complete hydrolysis. In the case of complete hydrolysis, theoretically, although 0.5 times mole of water of the total alkoxy group in the alkoxysilane is preferably added, water is more usually added than 0.5 times mole.

In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but is usually 0.5 to 2.5 times moles of the total alkoxy group in the alkoxydecane.

Again, usually, accelerates hydrolysis. For the purpose of the condensation reaction, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid, ammonia, methylamine, ethylamine, ethanolamine or triethyl may be used. A catalyst such as a base such as an amine or a metal salt of a mineral acid such as hydrochloric acid, sulfuric acid or nitric acid. In addition, under heating with a solution of alkoxysilane dissolved, and further promote hydrolysis. The condensation reaction is also a general practice. At this time, the heating temperature and the heating time can be appropriately selected as desired, and can be exemplified by heating at 50 ° C. Stir for 24 hours and heat under reflux. Stir for 1 hour, etc.

Further, as another method, a method of heating and polycondensing a mixture of alkoxysilane, a solvent and oxalic acid can be mentioned. Specifically, a method in which oxalic acid is added to an alcohol to form an alcohol solution of oxalic acid, and then the alkoxysilane is mixed while heating the solution. In this case, the amount of oxalic acid used is generally 0.2 to 2 moles per 1 mole of the total alkoxy group having an alkoxydecane. The heating in the method can be carried out at a liquid temperature of 50 to 180 ° C, preferably in the case where no liquid evaporation, vaporization or the like occurs, for example, in a vessel provided with a reflux pipe under reflux. A few ten to ten hours.

When a polyoxyalkylene oxide (A) is obtained, when a plurality of alkoxy decanes are used, they may be mixed as a mixture in which alkoxy decane is previously mixed, or a plurality of kinds of alkoxy decane may be sequentially mixed.

The solvent (hereinafter also referred to as a polymerization solvent) used in the polycondensation of the alkoxysilane is not particularly limited as long as it can dissolve the alkoxysilane. Further, even when the alkoxystane cannot be dissolved, it can be dissolved while the polycondensation reaction of the alkoxysilane is carried out. In general, since an alcohol is produced by a polycondensation reaction of an alkoxysilane, an organic solvent having good compatibility with an alcohol, an ethylene glycol, a glycol ether or an alcohol can be used.

Specific examples of such a polymerization solvent include methanol, ethanol, propanol, n-butanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexanediol, methyl cellosolve, and ethyl solution. Fiber, butyl cellosolve, ethyl carbitol, butyl carbitol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether , diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol Ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethyl Acetamide, γ-butyrolactone, dimethyl hydrazine, tetramethyl urea, hexamethyldiphosphoryl (phopho-) tridecylamine, m-cresol, and the like. Further, the ethylene glycol compound (B) described later can be used as a polymerization solvent.

Among them, as the polymerization solvent, methanol, ethanol, butyl cellosolve, hexanediol, 1,3-butanediol, 1,4-butanediol or such a mixed solvent is preferred. In the present invention, a plurality of types of the above-mentioned polymerization solvents may be mixed and used.

The polymerization solution of the polyoxane (A) obtained in this way (hereinafter also referred to as a polymerization solution) is generally converted into a SiO ₂ concentration by converting the ruthenium atom of the peralkoxy decane as a raw material (hereinafter referred to as a polymerization solution). In order to convert the SiO ₂ concentration.) as 0.5 to 20% by mass. By selecting any concentration in the concentration range, the formation of the gum can be suppressed, and a homogeneous solution can be obtained.

<Solution of Polyoxane (A)> In the present invention, the polymerization solution obtained by the above method can be used as a solution of polyoxane (A) as it is, or the solution obtained by the above method can be concentrated as needed. Adding a solvent to dilute or replace other solvents may also be used as a solution of polyoxyalkylene (A).

In this case, the solvent to be used (hereinafter also referred to as an additive solvent) may be the same as the solvent used in the polycondensation, or may be another solvent. The solvent is not particularly limited as long as it can dissolve the polyoxyalkylene oxide (A) in an average manner, and one type or plural types can be used arbitrarily.

Specific examples of such a solvent to be added include alcohols such as methanol, ethanol, 2-propanol, butanol, and diacetone; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ethylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, hexanediol, etc.; methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, propylene glycol monomethyl ether , glycol ethers such as propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; esters of methyl acetate, ethyl acetate, ethyl lactate, etc.; N-methyl-2-pyrrole Iridone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, dimethyl hydrazine, tetramethylurea, hexamethyldiphosphoryl Indoleamine, m-cresol and the like. Among them, in the case of adding a solvent, methanol, ethanol, butyl cellosolve, hexanediol, or a mixed solvent thereof is preferred.

In the present invention, one type or plural types of the polyoxyalkylene (A) solution obtained by the above method can be used.

<ethylene glycol compound (B)>

The ethylene glycol compound (B) used in the present invention has two carbon atoms which bond a hydroxyl group and a hydrogen atom, and the two carbon atoms have a structure which is bonded through an aliphatic group which may contain a hetero atom, and is continuous. The ethylene glycol compound has a carbon number of 3 to 6, preferably 3 to 5, particularly preferably 3 or 4. When the ethylene glycol compound (B) contains a hetero atom, it means a continuous ethylene glycol compound having 3 to 6 carbon atoms in addition to the hetero atom. For example, a particularly preferred specific example is a glycol compound (B) having a continuous carbon number of 4 in diethylene glycol.

The ethylene glycol compound (B) is not particularly limited as long as it is a compound as described above, and specific examples thereof include 1,3-propanediol, 1,3-butanediol, and 1,4-butane II. Alcohol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,6-hexanediol, diethylene Alcohol, dipropylene glycol, and the like.

Such an ethylene glycol compound (B) can be used as a solvent since it is usually liquid. Therefore, the polyaluminoxane (A) may be used as a polymerization solvent or an additive solvent in the polycondensation, or may be added after the polysiloxane (A) synthesized in another solvent.

The amount of the ethylene glycol compound (B) to be used in the present invention is 100 parts by mass based on the total of SiO ₂ in terms of the ruthenium atom of the peralkoxy decane used for obtaining the polyoxyalkylene oxide (A). 2.5 to 19,800 parts by mass, preferably 5 to 6,000 parts by mass, particularly preferably 25 to 4,000 parts by mass. When the amount of the ethylene glycol compound is less than 2.5 parts by mass, the water repellency effect of the liquid crystal alignment film cannot be sufficiently improved.

The ethylene glycol compound (B) used in the present invention can easily reduce the water repellency of the liquid crystal alignment film, and can reduce the organic group having a polysiloxane (A) in the liquid crystal alignment agent, and the obtained result is high compactness. A liquid crystal alignment film having a high hardness and a good liquid crystal alignment property of the film and excellent coatability.

<Solvent (C)> In the present invention, a solvent (C) having a solvent having a hydroxyl group and a compound different from the structure of the ethylene glycol compound (B) can be used.

Specific examples of the solvent (C) include alcohols such as methanol, ethanol, 2-propanol, butanol, and diacetone alcohol, ethylene glycol, 1,2-propanediol, and 1,2-butane. Ethylene glycols such as diol, 2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 2-methyl-2,4-pentanediol, and the like. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Glycol ether such as propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether A glycol ether acetate such as an acid ester, ethylene glycol monophenyl ether acetate or ethylene glycol monomethyl ether acetate. The solvent (C) is preferably ethanol, hexanediol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether or propylene glycol monobutyl ether.

The solvent (C) used in the present invention may be used as a polymerization solvent or an added solvent at the time of polycondensation of the polyoxyalkylene (A), or may be added to a polyoxyalkylene (A) in another solvent. )after that.

The solvent (C) can be improved in coating properties when a liquid crystal alignment agent is applied onto a substrate by viscosity adjustment of a liquid crystal alignment agent, spin coating, flexographic printing, or inkjet.

In the present invention, the amount of the solvent (C) used is 0 to 19,700 by mass based on 100 parts by mass of the total of SiO ₂ in terms of a ruthenium atom of the total alkoxy decane used to obtain the polyaluminoxane (A). More preferably, it is 0 to 19,600 parts by mass, and particularly preferably 0 to 18,800 parts by mass.

<Other components> In the present invention, the components other than the polysiloxane (A), the ethylene glycol compound (B) and the solvent (C), for example, inorganic fine particles, may be contained without impairing the effects of the present invention. A metalloxane oligomer, a metalloxane polymer, a leveling agent, and further a component such as a surfactant.

In the case of the inorganic fine particles, fine particles such as cerium oxide fine particles, alumina fine particles, titanium oxide fine particles, and magnesium fluoride fine particles are preferable, and a colloidal solution is particularly preferable. The colloidal solution may be one in which the inorganic fine particle powder is dispersed in a dispersion medium, or may be a colloidal solution of a commercially available product. In the present invention, the surface shape and other functions of the formed cured film can be imparted by containing inorganic fine particles. The inorganic fine particles preferably have an average particle diameter of 0.001 to 0.2 μm, particularly preferably 0.001 to 0.1 μm. When the average particle diameter of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured film formed using the prepared coating liquid may be lowered.

Examples of the dispersion medium of the inorganic fine particles include water and an organic solvent. The colloidal solution is preferably adjusted to have a pH or pKa of 1 to 10 from the viewpoint of stability of the coating liquid for film formation. More preferably 2~7.

As the organic solvent used for the dispersion medium of the colloidal solution, methanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, diethylene glycol, or the like can be used. An alcohol such as propylene glycol or ethylene glycol monopropyl ether; a ketone such as methyl ethyl ketone or methyl isobutyl ketone; an aromatic hydrocarbon such as toluene or xylene; dimethylformamide; An amide such as methyl acetamide or N-methylpyrrolidone; an ester such as ethyl acetate, butyl acetate or γ-butyrolactone; or an ether such as tetrahydrofuran or 1,4-dioxane. Among these, alcohols and ketones are preferred. These organic solvents may be used singly or in combination of two or more kinds as a dispersion medium.

Metalloxane oligomers, metalloxane polymers, can be used alone or in combination with precursors of tantalum, titanium, aluminum, lanthanum, cerium, lanthanum, tin, indium, zinc. The metalloxane oligomer, metalloxane polymer, may also be a commercially available product, which may be obtained by a conventional method such as hydrolysis from a metal alkoxide, a nitrate, a hydrochloride or a carboxylate. In the present invention, by containing a metalloxane oligomer and a metalloxane polymer, the refractive index of the hardened film can be increased to impart photosensitivity. When a metalloxane oligomer, a metalloxane polymer, can be used simultaneously in the synthesis of polyoxyalkylene (A), it can also be added after polyoxyalkylene (A).

A commercially available metalloxane oligomer, a metalloxane polymer, may be exemplified by methyl phthalate 51, methyl phthalate 53A, ethyl decanoate 40, ethyl decanoate manufactured by colcoat. 48, a hydrogen peroxide olefin oligomer such as EMS-485 or SS-101 or a lanthanane polymer, and a Titanoxane oligomer such as a titanium-n-butoxide tetramer manufactured by Kanto Chemical Co., Ltd. These may be used alone or in combination of two or more.

Further, a leveling agent, a surfactant, and the like can be used, and it is preferable to use a known product, and in particular, a commercially available product is relatively easy to obtain.

Further, in the polyoxane (A), the method of mixing the other components may be carried out simultaneously with the solution of the polyoxyalkylene (A) and the ethylene glycol compound (B), or after the mixing, Special restrictions.

<Preparation of Liquid Crystal Aligning Agent> The method of preparing the liquid crystal alignment agent of the present invention is not particularly limited. It is preferred that the polysiloxane (A) and the ethylene glycol compound (B) are in a state in which the solvent (C) and/or other components are uniformly mixed as needed.

Usually, polyoxyalkylene (A) is obtained in a solution state due to polycondensation in a solvent. Therefore, the method of using the polymerization solution of the polyoxyalkylene (A) described above as it is is simple. When the polymerization solvent of the polyoxyalkylene (A) is the ethylene glycol compound (B), the ethylene glycol compound (B) may not be added thereafter. Further, when the solution of the polyoxyalkylene (A) is not contained in the ethylene glycol compound (B), the ethylene glycol compound (B) may be added for use in preparing the liquid crystal alignment agent.

Further, when the solvent (C) is used in combination, it can be used as a polymerization solvent or an additive solvent in the synthesis of polysiloxane (A), or can be used in combination when adjusted to a liquid crystal alignment agent.

When the liquid crystal alignment agent is prepared, the polyoxyalkylene (A) is a liquid crystal alignment agent, and the argon atom of the peralkoxy decane used for obtaining the polyoxyalkylene (A) is converted into SiO _{2 in terms} of SiO _{2 .} It is 0.5 to 20% by mass, preferably 0.5 to 15% by mass, and particularly preferably 0.5 to 8% by mass. If it is in the range of such SiO ₂ equivalent concentration, it is easy to obtain a desired film thickness by one application, and it is also easy to obtain a sufficient pot life of the solution.

In addition, in this case, a solvent selected from the group consisting of a polymerization solvent selected from polyoxyalkylene (A), a solvent and a glycol compound (B) may be used as the solvent to be used for the adjustment of the concentration in terms of SiO ₂ .

<Formation of Liquid Crystal Alignment Film> The liquid crystal alignment agent of the present invention is dried by coating on a substrate. After firing, it can be a cured film.

The coating method of the liquid crystal alignment agent may, for example, be a spin coating method, a printing method, an inkjet method, a spray method, a roll coating method, or the like. However, in terms of a production surface, a transfer printing method is widely used in the industry. It is also suitable to use the liquid crystal alignment agent of the present invention.

The drying step after the application of the liquid crystal alignment agent is not absolutely necessary, and the drying step is preferably carried out after the application is completed until the time when the baking is not constant, or when the baking is not immediately performed after coating. In the drying, it is preferred that the solvent is removed to such an extent that the shape of the coating film is not deformed by the conveyance of the substrate, and the method of drying is not particularly limited. A method of drying at a temperature of 40 ° C to 150 ° C, preferably 60 ° C to 100 ° C, for 0.5 to 30 minutes, preferably 1 to 5 minutes, may be mentioned.

The coating film formed by coating the liquid crystal alignment agent by the above method is fired to form a cured film. In this case, the firing temperature may be carried out at any temperature of from 100 ° C to 350 ° C, but is preferably from 140 ° C to 300 ° C, more preferably from 150 ° C to 230 ° C, and particularly preferably from 160 ° C to 220 ° C. The firing time can be fired at any time from 5 minutes to 240 minutes. It is preferably 10 to 90 minutes, more preferably 20 to 90 minutes. The heating system is generally known, and for example, a hot plate, a hot air circulating oven, an IR oven, a belt furnace, or the like can be used.

The polyoxyalkylene (A) in the liquid crystal alignment film is subjected to polycondensation in the firing step. However, in the present invention, it is not necessary to completely polycondense without impairing the effects of the present invention. However, it is necessary to have a liquid crystal cell manufacturing process, and it is preferable to perform firing at a high temperature of 10 ° C or higher by heat treatment temperature such as curing of a sealant.

The thickness of the cured film can be selected as needed. When the thickness of the cured film is 5 nm or more, it is preferable because the reliability of the liquid crystal display element is easily obtained. More preferably, it is 10 nm or more. Further, when the thickness is 300 nm or less, the power consumption of the liquid crystal display element is extremely large, which is preferable. More preferably, it is 150 nm or less.

Such a cured film can be used as a liquid crystal alignment film as it is, and the cured film can be polished or irradiated with polarized light or light of a specific wavelength to perform treatment such as ion beam or the like to form a liquid crystal alignment film.

<Liquid crystal alignment film> It is considered that the liquid crystal alignment film of the present invention formed by the above method is a structure having a specific organic group of polysiloxane (A) and uneven distribution in the vicinity of the surface layer of the liquid crystal alignment film. . This case can be confirmed by measuring the water contact angle of the liquid crystal alignment film of the present invention. This case is presumed to be caused by the effect of the ethylene glycol compound (B) which is a component of the liquid crystal alignment agent of the present invention, and when the liquid crystal alignment agent contains the ethylene glycol compound (B), it is compared with the ethylene glycol-free compound ( When B), the water contact angle can be increased.

That is, it is considered that, due to the specific organic group of polysiloxane (A), due to the effect of the ethylene glycol compound (B), uneven distribution is distributed in the vicinity of the surface layer of the liquid crystal alignment film, and liquid crystal molecules are easy to be used. The effect of alignment in one direction, especially in the vertical direction. Therefore, the liquid crystal alignment film of the present invention can exhibit good liquid crystal vertical alignment property due to the high water repellency.

Further, in the liquid crystal alignment film of the present invention, even when the amount of the specific organic group having the polyoxyalkylene (A) as a component of the liquid crystal alignment agent of the present invention is small, since the liquid crystal alignment film has high water repellency, it has a good The liquid crystal has vertical alignment, high density, and high hardness. Further, since the liquid crystal alignment film is obtained from the liquid crystal alignment agent of the present invention having excellent coatability, it has an effect of high uniformity. Therefore, it is possible to provide a liquid crystal display element with high reliability and high image quality. Specifically, the liquid crystal alignment agent of the present invention has a specific organic group of polyoxyalkylene (A), and the obtained liquid crystal is 0.1 to 30 moles per 100 moles of the germanium atom having a polyoxyalkylene (A). The alignment film has high water repellency, exhibits good liquid crystal vertical alignment, and has high density, high hardness, and excellent uniformity.

Further, the display element having the liquid crystal alignment film can reduce the content of the specific organic group having the polyoxyalkylene (A) due to the action of the ethylene glycol compound (B) contained in the liquid crystal alignment agent. I believe that the absolute value of the accumulated charge of the display element can be made small.

<Liquid Crystal Display Element> The liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method, and then forming a liquid crystal cell by a known method. Here, an example of the liquid crystal cell formation is generally a method in which a pair of substrates formed by a liquid crystal alignment film are sandwiched by a spacer, fixed by a sealant, and filled with a liquid crystal to be closed. At this time, the size of the spacer used is 1 to 30 μm, but preferably 2 to 10 μm.

The method of injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method in which a liquid crystal cell is produced in a reduced pressure, and a liquid crystal is injected into the liquid crystal, and the liquid crystal is dropped and then closed.

The substrate used for the liquid crystal display device is not particularly limited as long as it is a substrate having high transparency, and is usually a substrate formed on a substrate to drive a transparent electrode for liquid crystal.

Specific examples thereof include glass plates, polycarbonates, poly(meth)acrylates, polyether oximes, polyarylates, polyurethanes, polybenzazoles, polyethers, polyetherketones, and the like. Trimethylpentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triethylenesulfonyl cellulose, diethyl cellulose, acetate butyrate cellulose, etc. The substrate on which the transparent electrode is formed.

Further, in a high-performance element such as a TFT-type element, an object such as a transistor is used between the electrode for driving the liquid crystal and the substrate.

In the case of a transmissive liquid crystal element, a substrate as described above is generally used. However, if the reflective liquid crystal display element is only a single-sided substrate, an opaque substrate such as a germanium wafer may be used. At this time, for example, an aluminum material capable of reflecting light may be used for the electrode formed on the substrate.

As described above, the liquid crystal alignment film obtained by using the liquid crystal alignment agent of the present invention has high compactness, high hardness, high water repellency of the film, and good liquid crystal vertical alignment, and excellent uniformity. Liquid crystal alignment film. Further, an element made of the liquid crystal alignment film described above has a good charge-accumulation property.

Example

The present invention will be specifically described below by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples.

The description of the abbreviations in this embodiment.

TEOS: Tetraethoxydecane C8: Octyltriethoxydecane C12: Dodecyltriethoxydecane C18: Octadecyltriethoxydecane F13: Tridecafluorooctyltrimethoxydecane MTES: A Triethoxy decane MPS: 3-Hydroxythiopropyltrimethoxydecane MAPS: 3-methylpropenyloxypropyltrimethoxydecane HG: hexanediol (2-methyl-2,4- Pentanediol) BCS: butyl cellosolve EtOH: ethanol 1,3-PrDO: 1,3-propanediol 1,3-BDO: 1,3-butanediol 1,4-BDO: 1,4- Butanediol 1,3-PeDO: 1,3-pentanediol 1,6-HDO: 1,6-hexanediol DEG: Diethylene glycol DPG: Dipropylene glycol

<Synthesis Example 1> Into a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, 164.3 g of HG, 164.9 g of TEOS, and 13.9 g of C12 were placed and stirred to prepare a solution of an alkoxydecane monomer. To the solution, 82.1 g of HG, 74.1 g of water, and 0.8 g of oxalic acid as catalyzed oxalic acid solution were mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then allowed to cool to obtain a polyoxoxane solution (K1) having a solid content concentration of 10% by mass in terms of SiO ₂ .

<Preparation Examples 1 to 7> With respect to 10 g of the polyaluminoxane solution (K1) obtained in Synthesis Example 1, by mixing and stirring the amounts of HG and BCS and the solvent (X) shown in Table 1, the solvent composition was as follows. As shown in Table 1, a liquid crystal alignment agent (KL1 to KL7) having a solid content concentration of 4% by mass in terms of SiO ₂ was obtained.

<Preparation Example 8> 10 g of the polyaluminoxane solution (K1) obtained in Synthesis Example 1 and HG11.0 g and BCS 4.0 g were mixed and stirred so that the solvent composition became HG: BCS = 80:20, and the solid content concentration in terms of SiO ₂ was obtained. It is a 4% by mass liquid crystal alignment agent (KM1).

<Synthesis Example 2> Into a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, 164.3 g of BCS, 164.9 g of TEOS and C12, and 13.9 g of TEOS were charged, and stirred, and a solution of alkoxy decane monomer was prepared. To the solution, 82.1 g of BSC, 74.1 g of water, and 0.8 g of oxalic acid as catalyzed oxalic acid solution were mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then allowed to cool to obtain a polyoxysilane solution (K2) having a solid content concentration of 10% by mass in terms of SiO ₂ .

<Preparation Example 9> In 10 g of the polyaluminoxane solution (K2) obtained in Synthesis Example 2, 13.0 g of BCS and 2.0 g of DEG were added, and the mixture was stirred and mixed to have a solvent composition of BCS: DEG = 90:10 to obtain SiO _{2 .} A liquid crystal alignment agent (KL8) having a solid content concentration of 4% by mass was converted.

<Preparation Example 10> In 10 g of the polyaluminoxane solution (K2) obtained in Synthesis Example 2, 15.0 g of BCS was mixed and stirred to obtain a liquid crystal alignment agent (KM2) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 3> Into a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, 164.3 g of DEG, 164.9 g of TEOS, and 13.9 g of C12 were placed and stirred to prepare a solution of alkoxysilane monomer. To the solution, 82.1 g of DEG, 74.1 g of water, and 0.8 g of oxalic acid solution of oxalic acid as a catalyst were mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then allowed to cool to obtain a polysiloxane solution (K3) having a solid content concentration of 10% by mass in terms of SiO ₂ .

<Preparation Example 11> In 10 g of the polyaluminoxane solution (K3) obtained in Synthesis Example 3, 15.0 g of DEG was mixed and stirred to obtain a liquid crystal alignment agent (KL9) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Preparation Example 12> In 10 g of the polyoxane solution (K3) obtained in Synthesis Example 3, 13.0 g of DEG and 2.0 g of BCS were added and mixed, and the solvent composition was changed to BCS: DEG = 10:90, and SiO ₂ conversion was obtained. A liquid crystal alignment agent (KL1O) having a solid concentration of 4% by mass.

<Synthesis Example 4> Into a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, 164.3 g of EtOH, 164.9 g of TEOS, and 13.9 g of C12 were placed and stirred to prepare a solution of an alkoxydecane monomer. To the solution, 82.1 g of EtOH, 74.1 g of water, and 0.8 g of oxalic acid as catalyzed oxalic acid solution were mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then allowed to cool to obtain a polyoxane solution (K4) having a solid content concentration of 10% by mass in terms of SiO ₂ .

<Preparation Example 13> In 10 g of the polyaluminoxane solution (K4) obtained in Synthesis Example 4, 13.0 g of EtOH and 2.0 g of DEG were added and mixed, and the solvent composition was EtOH: DEG = 90:10, and SiO ₂ conversion was obtained. A liquid crystal alignment agent (KL11) having a solid content concentration of 4% by mass.

<Preparation Example 14> 15.0 g of EtOH was mixed with 10 g of the polyoxoxane solution (K4) obtained in Synthesis Example 4 to obtain a liquid crystal alignment agent (KM3) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 5> Into a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, 121.0 g of HG, 40.3 g of BCS, 164.9 g of TEOS, and 17.4 g of C18 were placed and stirred to prepare a solution of an alkoxydecane monomer. In this solution, 60.5 g of HG, 20.2 g of BCS, 75.0 g of water, and 0.8 g of oxalic acid as catalyzed oxalic acid solution were mixed in advance, and the mixture was dropped at room temperature for 30 minutes, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. . Thereafter, the mixture was heated under reflux for 1 hour, and then allowed to cool to obtain a polyoxoxane solution (K5) having a solid content concentration of 10% by mass in terms of SiO ₂ .

<Preparation Examples 15 to 19> HG and BCS and DEG in an amount shown in Table 2 to be mixed and stirred with respect to 10 g of the polyaluminoxane solution (K5) obtained in Synthesis Example 5, and the solvent composition is shown in Table 2. Further, a liquid crystal alignment agent (KL12 to KL15 and KM4) having a solid content concentration of 4% by mass in terms of SiO ₂ was obtained.

<Synthesis Example 6> In a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, 124.4 g of HG, 41.5 g of BCS, 164.9 g of TEOS, and 11.5 g of C8 were placed and stirred to prepare a solution of an alkoxydecane monomer. In this solution, 62.2 g of HG, 20.7 g of BCS, 74.1 g of water, and 0.8 g of oxalic acid of oxalic acid as a catalyst were mixed in advance, and the mixture was dropped at room temperature for 30 minutes, and after completion of the dropwise addition, it was stirred at room temperature for 30 minutes. . Thereafter, the mixture was heated under reflux for 1 hour, and then allowed to cool to obtain a polyoxysilane solution (K6) having a solid content concentration of 10% by mass in terms of SiO ₂ .

<Preparation Example 20> 10.3 g of HG, 2.8 g of BCS and 2.0 g of DEG were added to 10 g of the polyaluminoxane solution (K6) obtained in Synthesis Example 6, and the mixture was stirred to make the solvent composition HG: BCS: DEG = 70:20:10, a liquid crystal alignment agent (KL16) having a solid content concentration of 4% by mass in terms of SiO ₂ was obtained.

<Preparation Example 21> In 10 g of the polyaluminoxane solution (K6) obtained in Synthesis Example 6, 12.2 g of HG and 2.8 g of BCS were added and mixed, and the solvent composition was changed to HG: BCS = 80:20 to obtain SiO. ₂ A liquid crystal alignment agent (KM5) having a solid content concentration of 4% by mass.

<Synthesis Example 7> In a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, 118.1 g of HG, 39.4 g of BCS, 207.3 g of TEOS, and 1.7 g of C12 were placed, and stirred to prepare a solution of alkoxysilane monomer. In this solution, 59.0 g of HG, 19.7 g of BCS, 53.9 g of water, and 0.9 g of oxalic acid solution of oxalic acid as a catalyst were mixed in advance for 30 minutes at room temperature, and stirred at room temperature for 30 minutes after completion of the dropwise addition. . Thereafter, the mixture was heated under reflux for 1 hour, and then allowed to cool to obtain a polyoxysilane solution (K7) having a solid content concentration of 12% by mass in terms of SiO ₂ .

<Preparation Example 22> In 10 g of the polyaluminoxane solution (K7) obtained in Synthesis Example 7, 13.8 g of HG, 3.8 g of BCS and 2.5 g of DEG were added and mixed, and the solvent composition was changed to HG: BCS: DEG = 70: 20:10, a liquid crystal alignment agent (KL17) having a solid content concentration of 4% by mass in terms of SiO ₂ was obtained.

<Preparation Example 23> In 10 g of the polyaluminoxane solution (K7) obtained in Synthesis Example 7, 16.2 g of HG and 3.8 g of BCS were added and mixed, and the solvent composition was changed to HG:BCS=80:20 to obtain SiO ₂ conversion. A liquid crystal alignment agent (KM6) having a solid content concentration of 4% by mass.

<Synthesis Example 8> Into a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, 124.9 g of HG, 41.6 g of BCS, 171.9 g of TEOS and 2.8 g of C12 were placed, and stirred to prepare a solution of alkoxydecane monomer. In this solution, 62.5 g of HG, 20.8 g of BCS, 74.8 g of water, and 0.8 g of oxalic acid as catalyzed oxalic acid were mixed in advance for 30 minutes at room temperature, and stirred at room temperature for 30 minutes after completion of the dropwise addition. . Thereafter, the mixture was heated under reflux for 1 hour, and then allowed to cool to obtain a polyoxyalkylene solution (K8) having a solid content concentration of 10% by mass in terms of SiO ₂ .

<Preparation Example 24> 10 g of HG was added to 10 g of the polyoxane solution (K8) obtained in Synthesis Example 8, and 2.8 g of BCS and 2.0 g of DEG were mixed and stirred to make the solvent composition HG: BCS: DEG = 70:20:10, a liquid crystal alignment agent (KL18) having a solid content concentration of 4% by mass in terms of SiO ₂ was obtained.

<Preparation Example 25> In 10 g of the polyaluminoxane solution (K8) obtained in Synthesis Example 8, 12.2 g of HG and 2.8 g of BCS were added and mixed, and the solvent composition was changed to HG: BCS = 80:20 to obtain SiO. ₂ A liquid crystal alignment agent (KM7) having a solid content concentration of 4% by mass.

<Synthesis Example 9> Into a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, 123.2 g of HG, 41.1 g of BCS, 164.9 g of TEOS, and 13.9 g of C12 were placed and stirred to prepare a solution of an alkoxydecane monomer. In this solution, 61.6 g of HG, 20.5 g of BCS, 74.1 g of water, and 0.8 g of oxalic acid as catalyzed oxalic acid were mixed in advance for 30 minutes at room temperature, and stirred at room temperature for 30 minutes after completion of the dropwise addition. . Thereafter, the mixture was heated at 65 ° C for 1 hour, and then allowed to cool to obtain a polysiloxane solution (K9) having a solid content concentration of 10% by mass in terms of SiO ₂ .

<Preparation Example 26> 10.3 g of HG, 2.8 g of BCS and 2.0 g of DEG were added to 10 g of the polyaluminoxane solution (K9) obtained in Synthesis Example 9, and the mixture was stirred to make the solvent composition HG: BCS: DEG = 70:20:10, a liquid crystal alignment agent (KL19) having a solid content concentration of 4% by mass in terms of SiO ₂ was obtained.

<Preparation Example 27> In 10 g of the polyaluminoxane solution (K9) obtained in Synthesis Example 9, 12.2 g of HG and 2.8 g of BCS were added and mixed, and the solvent was made into HG: BCS = 80:20 to obtain SiO. ₂ A liquid crystal alignment agent (KM8) having a solid content concentration of 4% by mass.

<Synthesis Example 10> In a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, 119.0 g of HG, 39.6 g of BCS, 147.6 g of TEOS, and 41.6 g of C12 were placed, and stirred to prepare a solution of an alkoxydecane monomer. In this solution, 59.5 g of HG, 19.8 g of BCS, 72.2 g of water, and 0.8 g of oxalic acid solution of oxalic acid as a catalyst were mixed in advance, and the mixture was dropped at room temperature for 30 minutes, and after completion of the dropwise addition, it was stirred at room temperature for 30 minutes. . Thereafter, the mixture was heated under reflux for 1 hour, and then allowed to cool to obtain a polysiloxane solution (K10) having a solid content concentration of 10% by mass in terms of SiO ₂ .

<Preparation Example 28> In 10 g of the polyaluminoxane solution (K10) obtained in Synthesis Example 10, 10.3 g of HG, 2.8 g of BCS and 2.0 g of DEG were added and stirred to make the solvent composition HG: BCS: DEG = 70:20:10, a liquid crystal alignment agent (KL20) having a solid content concentration of 4% by mass in terms of SiO ₂ was obtained.

<Preparation Example 29> In 10 g of the polyaluminoxane solution (K10) obtained in Synthesis Example 10, 12.2 g of HG and 2.8 g of BCS were added and mixed, and the solvent composition was changed to HG: BCS = 80:20 to obtain SiO. ₂ A liquid crystal alignment agent (KM9) having a solid content concentration of 4% by mass.

<Synthesis Example 11> Into a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, 116.8 g of HG, 39.0 g of BCS, 138.9 g of TEOS, and 55.4 g of C12 were charged to prepare a solution of an alkoxydecane monomer. In this solution, 58.4 g of HG, 19.5 g of BCS, 71.2 g of water, and 0.8 g of oxalic acid of oxalic acid as a catalyst were mixed in advance, and the mixture was dropped at room temperature for 30 minutes, and after completion of the dropwise addition, it was stirred at room temperature for 30 minutes. . Thereafter, the mixture was heated under reflux for 1 hour, and then allowed to cool to obtain a polysiloxane solution (K11) having a solid content concentration of 10% by mass in terms of SiO ₂ .

<Preparation Example 30> In 10 g of the polyaluminoxane solution (K11) obtained in Synthesis Example 11, 10.3 g of HG, 2.8 g of BCS and 2.0 g of DEG were added and stirred to make the solvent composition HG: BCS: DEG = 70:20:10, a liquid crystal alignment agent (KL21) having a solid content concentration of 4% by mass in terms of SiO ₂ was obtained.

<Preparation Example 31> In 10 g of the polyaluminoxane solution (K11) obtained in Synthesis Example 11, 12.2 g of HG and 2.8 g of BCS were added and mixed, and the solvent was made into HG: BCS = 80:20 to obtain SiO. ₂ A liquid crystal alignment agent (KM1O) having a solid content concentration of 4% by mass.

<Synthesis Example 12> 123.2 g of HG, 41.1 g of BCS, 164.9 g of TEOS, and 13.9 g of C12 were placed in a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, and stirred to prepare a solution of alkoxysilane monomer. In this solution, 61.6 g of HG, 20.5 g of BCS, 74.1 g of water, and 0.8 g of oxalic acid as catalyzed oxalic acid were mixed in advance for 30 minutes at room temperature, and stirred at room temperature for 30 minutes after completion of the dropwise addition. . Thereafter, the mixture was heated under reflux for 1 hour, and then allowed to cool to obtain a polyoxyalkylene solution (K12) having a solid content concentration of 10% by mass in terms of SiO ₂ .

<Preparation Example 32> In 10 g of the polyaluminoxane solution (K12) obtained in Synthesis Example 12, 10.2 g of HG, 2.8 g of BCS and 2.0 g of DEG were added and mixed, and the solvent was made into HG: BCS: DEG = 70:20:10, a liquid crystal alignment agent (KL22) having a solid content concentration of 4% by mass in terms of SiO ₂ was obtained.

<Preparation Example 33> In 10 g of the polyoxane solution (K12) obtained in Synthesis Example 12, 12.2 g of HG and 2.8 g of BCS were added and mixed, and the solvent was made into HG: BCS = 80:20 to obtain SiO. ₂ A liquid crystal alignment agent (KM11) having a solid content concentration of 4% by mass.

<Synthesis Example 13> 124.3 g of HG, 41.4 g of BCS, 156.3 g of TEOS, 13.9 g of C12, and 7.4 g of MTES were placed in a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, and stirred to prepare an alkoxydecane single. Body solution. In this solution, 62.1 g of HG, 20.7 g of BCS, 73.1 g of water, and 0.8 g of oxalic acid as catalyzed oxalic acid solution were mixed in advance, and the mixture was dropped at room temperature for 30 minutes, and after completion of the dropwise addition, it was stirred at room temperature for 30 minutes. . Thereafter, the mixture was heated under reflux for 1 hour, and then allowed to cool to obtain a polyoxoxane solution (K13) having a solid content concentration of 10% by mass in terms of SiO ₂ .

<Preparation Example 34> 10.3 g of HG, 2.8 g of BCS and 2.0 g of DEG were added to 10 g of the polyoxoxane solution (K13) obtained in Synthesis Example 13, and the mixture was stirred and stirred to make the solvent composition HG: BCS: DEG =70:20:10, a liquid crystal alignment agent (KL23) having a solid content concentration of 4% by mass in terms of SiO ₂ was obtained.

<Preparation Example 35> In 10 g of the polyaluminoxane solution (K13) obtained in Synthesis Example 13, 12.2 g of HG and 2.8 g of BCS were added, and the mixture was stirred and stirred to obtain a solvent composition of HG:BCS=80:20. A liquid crystal alignment agent (KM12) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 14> In a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, 13 g of HG, 43.4 g of BCS, 147.6 g of TEOS, 13.9 g of C12, 8.18 g of MPS and 10.4 g of MAPS were placed, and the mixture was stirred to prepare an alkane. A solution of a oxoxane monomer. In this solution, 65.1 g of HG, 21.7 g of BCS, 69.4 g of water, and 0.8 g of oxalic acid as catalyzed oxalic acid solution were mixed in advance for 30 minutes at room temperature, and stirred at room temperature for 30 minutes after completion of the dropwise addition. . Thereafter, the mixture was heated under reflux for 1 hour, and then allowed to cool to obtain a polysiloxane solution (K14) having a solid content concentration of 10% by mass in terms of SiO ₂ .

<Preparation Example 36> In 10 g of the polyaluminoxane solution (K14) obtained in Synthesis Example 14, 10.2 g of HG, 2.7 g of BCS and 2.0 g of DEG were added and stirred, and the solvent was made into HG: BCS: DEG = 70:20:10, a liquid crystal alignment agent (KL24) having a solid content concentration of 4% by mass in terms of SiO ₂ was obtained.

<Preparation Example 37> In 10 g of the polyaluminoxane solution (K14) obtained in Synthesis Example 14, 12.3 g of HG and 2.7 g of BCS were added and mixed, and the solvent composition was changed to HG: BCS = 80:20 to obtain SiO. ₂ A liquid crystal alignment agent (KM13) having a solid content concentration of 4% by mass.

<Synthesis Example 15> Into a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, 120.4 g of HG, 40.1 g of BCS, 164.9 g of TEOS, and 19.5 g of F13 were placed, and stirred, and a solution of alkoxysilane monomer was prepared. In this solution, 60.2 g of HG, 20.1 g of BCS, 74.1 g of water, and 0.8 g of oxalic acid as a catalyst were added in advance, and the mixture was dropped at room temperature for 30 minutes, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. . Thereafter, the mixture was heated under reflux for 1 hour, and then allowed to cool to obtain a polyoxoxane solution (K15) having a solid content concentration of 10% by mass in terms of SiO ₂ .

<Preparation Example 38> In 10 g of the polyaluminoxane solution (K15) obtained in Synthesis Example 15, 12.2 g of HG and 2.8 g of BCS were added and mixed, and the solvent composition was changed to HG: BCS = 80:20 to obtain SiO. ₂ A liquid crystal alignment agent (KM14) having a solid content concentration of 4% by mass.

<Preparation Example 39> 10.3 g of HG, 2.7 g of BCS and 2.0 g of DEG were added to 10 g of the polyoxane solution (K15) obtained in Synthesis Example 15 and mixed, and the solvent was made into HG: BCS: DEG = 70:20:10, a liquid crystal alignment agent (KL25) having a solid content concentration of 4% by mass in terms of SiO ₂ was obtained.

<Preparation Example 40> 9 g of a liquid crystal alignment agent (KL22) obtained by the same method as in Preparation Example 32, and colloidal ceria having a particle size of 18 nm in an organic solvent (HG: BCS: DEG = 70: 20: 10) 1 g of a dispersed ceria gel (4% by mass in terms of solid content in terms of SiO ₂ ) was mixed and stirred to obtain a liquid crystal alignment agent (KL26) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Preparation Example 41> 9 g of a liquid crystal alignment agent (KM11) obtained by the same method as in Preparation Example 33, and a colloidal ceria having a particle size of 18 nm dispersed in an organic solvent (HG: BCS = 80: 20) 1 g of a cerium oxide gel (containing 4 masses in terms of solid content of SiO ₂ ) was mixed and stirred to obtain a liquid crystal alignment agent (KM15) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 16> Into a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, 300.6 g of EtOH was charged, and 90.0 g of oxalic acid was added to EtOH in a small amount with stirring to prepare an EtOH solution of oxalic acid. The solution was then heated to its reflux temperature, and a mixture of TEOS 99.0 g and C18 was added dropwise to a solution of 10.4 g for 30 minutes under reflux. After the completion of the dropwise addition, the mixture was further heated under reflux for 5 hours, and then allowed to cool to obtain a polyoxymethane solution (K16) having a SiO ₂ solid content concentration of 6 mass%.

<Preparation Example 42> In 10 g of the polyoxane solution (K16) obtained in Synthesis Example 16, 1.1 g of BCS and 3.9 g of EtOH were added, mixed and stirred to obtain a solvent composition of EtOH: BCS = 90:10. A liquid crystal alignment agent (KM16) having a SiO ₂ solid content concentration of 4% by mass was converted.

<Preparation Example 43> To 10 g of the polyaluminoxane solution (K16) obtained in Synthesis Example 16, 1.1 g of DEG and 3.9 g of EtOH were added, mixed and stirred to obtain a solvent composition of EtOH: DEG = 90:10. A liquid crystal alignment agent (KL27) having a SiO ₂ solid content concentration of 4% by mass was converted.

<Examples 1 to 27> The liquid crystal alignment agents KL1 to KL27 were pressure-filtered by a membrane filter having a pore diameter of 0.45 μm, and then formed on a glass substrate with an ITO transparent electrode by spin coating. The substrate was dried on a hot plate at 80 ° C for 5 minutes, and then fired in a hot air circulating type dust-free oven at 180 ° C for 60 minutes to form a liquid crystal alignment film having a film thickness of about 80 nm. Further, the water contact angle of the liquid crystal alignment film was measured by a method described later. The results are shown in Table 3.

<Comparative Examples 1 to 16> The liquid crystal alignment agents KM1 to KM16 were pressure-filtered by a membrane filter having a pore diameter of 0.45 μm, and then formed on a glass substrate with an ITO transparent electrode by spin coating. The substrate was dried on a hot plate at 80 ° C for 5 minutes, and then fired in a hot air circulating type dust-free oven at 180 ° C for 60 minutes to form a liquid crystal alignment film having a film thickness of about 80 nm. Further, the water contact angle of the liquid crystal alignment film was measured by a method described later. The results are shown in Table 3.

[Water contact angle] 3 μL of pure water was dropped on the liquid crystal alignment films obtained in Examples 1 to 27 and Comparative Examples 1 to 16, and the contact angle was measured using an automatic contact angle meter CA-Z type manufactured by Kyowa Interface Science Co., Ltd.

It can be seen from Table 3 that although the same polyoxane solution is used as the liquid crystal alignment agent, it contains 1,3-PrDO, 1,3-BDO, 1,4-BDO, 1,3-PeDO, 1,6-HDO. When the specific ethylene glycol compound such as DEG, DPG, or the like is used, the water contact angle of the film at the time of film formation becomes self-evident as compared with the case where the liquid crystal alignment agent is not contained. For example, it is apparent from the comparison of Examples 1 to 7 of K1 using a polyoxyalkylene solution with Comparative Example 1. That is, the liquid crystal alignment agent enhances the water repellency of the film under the above-described specific ethylene glycol compound.

<Example 27> Using the liquid crystal alignment agent KL18 obtained in Preparation Example 24, a liquid crystal cell was produced by the method described later. The liquid crystal cell obtained by the method described later was confirmed to have liquid crystal alignment properties. The results are shown in Table 4.

<Comparative Example 16> Using a liquid crystal alignment agent KM7 obtained in Preparation Example 25, a liquid crystal cell was produced by a method described later. The liquid crystal cell obtained by the method described later was confirmed to have liquid crystal alignment properties. The results are shown in Table 4.

[Preparation of liquid crystal cell] Two sheets of the substrate with the liquid crystal alignment film obtained by the above method are prepared, and a spacer having a particle diameter of 6 μm is spread on the liquid crystal alignment film surface of one of the substrates, and then a mesh is formed on the outer edge of the substrate. After the epoxy-based adhesive is applied by the printing method, the liquid crystal alignment film is adhered to a face-to-face manner, and after pressing, it is hardened to form an empty cell. In the empty cell, MLC-6608 (trade name) manufactured by Merk Co., Ltd. was injected by a vacuum injection method, and the injection hole was sealed with a UV curable resin to prepare a liquid crystal cell (element).

[Liquid Crystal Alignment] The liquid crystal cell prepared by the above-described method of [liquid crystal cell production] was observed under a polarizing microscope, and the alignment state of the liquid crystal was confirmed. The liquid crystal cell has no defects in its entirety, and is represented by ○ for the average alignment state, aligning defects for one of the liquid crystal cells, and × for the non-vertical alignment. The results are shown in Table 4.

As described in the foregoing Table 3, even if the same polyoxyalkylene solution was used, a liquid crystal alignment film prepared by using a liquid crystal alignment agent (Comparative Example 16) containing no specific ethylene glycol compound such as DEG was used as compared with the use. The liquid crystal alignment film produced by the liquid crystal alignment agent (Example 27) of the specific ethylene glycol compound of DEG has a water contact angle which is not high. As can be seen from Table 4, the liquid crystal cell produced by using the liquid crystal alignment film can be sufficiently vertical if a liquid crystal cell of a liquid crystal alignment film produced by using a liquid crystal alignment agent such as a specific ethylene glycol compound of DEG is used. Liquid crystal alignment property, if a liquid crystal cell of a liquid crystal alignment film produced by a liquid crystal alignment agent which does not contain a specific ethylene glycol compound such as DEG is used, sufficient vertical liquid crystal alignment property cannot be obtained.

<Examples 28 to 29> The liquid crystal alignment agent KL19 obtained in Preparation Example 26 or the liquid crystal alignment agent KL20 obtained in Preparation Example 28 was pressure-filtered by a membrane filter having a pore diameter of 0.45 μm, and then attached with an ITO transparent electrode. Each of the glass substrates was formed into a film by a spin coating method and a printing method. The substrate was dried on a hot plate at 80 ° C for 5 minutes, and then fired in a hot air circulating type dust-free oven at 180 ° C for 60 minutes to form a liquid crystal alignment film having a film thickness of about 80 nm. In the meantime, the coating property at the time of film formation is evaluated by a method (coating property of spin coating, coating property of flexographic printing) which will be described later. Moreover, the pencil hardness is measured by the method mentioned later. Further, a substrate on which a liquid crystal alignment film is attached is prepared by a method of forming the liquid crystal cell, and a liquid crystal cell is prepared, and the accumulated charge is measured by a method described later. The results are shown in Table 5.

<Comparative Examples 17 to 18> The liquid crystal alignment agent KM9 obtained in Preparation Example 29 or the liquid crystal alignment agent KM8 obtained in Preparation Example 27 was used, and the coating properties were carried out in the same manner as in Examples 28 to 29, which will be described later. Pencil hardness. Determination of accumulated charge. The results are shown in Table 5.

[Pencil Hardness] The liquid crystal alignment films obtained in Examples 28 to 29 and Comparative Examples 17 to 18 were measured by a pencil hardness test method (JIS K5400). The results are shown in Table 5.

[Coating property of spin coating] The liquid crystal alignment agent was filtered through a chromato disk (having a pore diameter of 0.45 μm), and then formed on a glass substrate with an ITO transparent electrode by a spin coating method. The substrate was dried on a hot plate at 80 ° C for 5 minutes, and then fired in a hot air circulating type dust-free oven at 180 ° C for 60 minutes to form a liquid crystal alignment film having a film thickness of about 80 nm. The obtained liquid crystal alignment film was visually observed, and there was no pinhole in the hardened film. In the case of unevenness, it is indicated by ○, and part of it is pinhole. When the unevenness is expressed by △, all pinholes are generated. The case of unevenness is indicated by ×. The results are shown in Table 5.

[Coating property of flexographic printing] The liquid crystal alignment agent was filtered through a chromatographic disk (having a pore size of 0.45 μm), and then a DR printing machine ANILOX ROLL (360#) letterpress (Daily Point 400 L 30% 70 degrees) manufactured by Nippon Photo Printing Co., Ltd. was used. A coating film is formed on the glass substrate with the ITO transparent electrode. The coating film was dried on a hot plate at a temperature of 80 ° C for 5 minutes, and then fired in a hot air circulating type dust-free oven at 180 ° C for 60 minutes to form a liquid crystal alignment film. The obtained liquid crystal alignment film was visually observed and hardened on the film to be pinhole free. In the case of a good unevenness, indicated by ○, a part of the pinhole is produced. In the case of unevenness, indicated by △, all pinholes are produced. The case of unevenness is indicated by ×. The results are shown in Table 5.

[Accumulation charge measurement method] On a liquid crystal cell, a 30 Hz/±2.8 V rectangular wave having a DC of 10 V was applied at a temperature of 23 ° C for 20 hours, and after a DC of 10 V was cut off, the optical flicker (fliker) elimination method was immediately determined. The accumulated voltage remaining in the liquid crystal cell. The results are shown in Table 5.

As can be seen from Table 5, when the liquid crystal alignment agent is formed from a liquid crystal alignment agent (Comparative Example 17) which does not contain a specific ethylene glycol compound such as DEG, the coating property of the liquid crystal alignment film, whether it is a spin coating method or a flexible sheet Printing, will produce pinholes. The situation is uneven, so it is not sufficient. Moreover, the pencil hardness of the film is also as low as H is self-evident. Further, after the accumulated charge was applied for 20 hours and DC was turned off for 10 minutes, the amount of change was small, and it was found that the removal rate of the accumulated charges was slow. Therefore, it can be seen that when the liquid crystal alignment agent is formed from a liquid crystal alignment agent (Example 28) containing a specific solvent such as DEG, the coating property of the liquid crystal alignment film, whether it is a spin coating method. In the flexo printing, no pinholes were found. In the case of unevenness, it is sufficient. Moreover, the pencil hardness of the film is also as high as 6H. Further, since the absolute value of the accumulated electric charge was also greatly reduced after the DC for 20 hours was applied and 10 minutes after the DC was turned off, it was found that the removal rate of the accumulated electric charge was fast. That is, we can speculate on the burn marks that can characterize the components. Problems such as persistence of vision can be reduced.

It can be seen that the liquid crystal alignment agent system can obtain good coating properties when a vertical liquid crystal alignment film having a high water contact angle is obtained by containing a specific ethylene glycol compound such as DEG. High hardness. A vertical liquid crystal alignment film with good DC residual characteristics. This is a liquid crystal alignment agent that provides high reliability by containing a specific solvent such as DEG. High-quality vertical liquid crystal display elements.

Industrial use possibility

When the liquid crystal alignment agent of the present invention contains a specific solvent, the water repellency of the film can be easily improved at the time of film formation as compared with the use of the liquid crystal alignment agent without such a film, and as a result, high density and high hardness can be formed. A liquid crystal alignment film having a good liquid crystal alignment property.

Further, the liquid crystal alignment agent of the present invention is excellent in coatability, and a liquid crystal alignment film having high uniformity can be obtained. Therefore, it is possible to provide a liquid crystal display element with high reliability and high image quality.

Further, when a liquid crystal alignment agent is prepared, the water repellency of the film can be increased by adding a specific ethylene glycol compound, and the long-chain alkyl group-containing decane used for obtaining a liquid crystal alignment film which exhibits desired water repellency can be used. The amount can be reduced, so it is more economical.

Therefore, various liquid crystal alignment elements, particularly vertical alignment type (VA), can be suitably used. It can also be used for other polarizing films, retardation films, and alignment films for viewing angle expansion films.

In addition, the specification of the Japanese Patent Application No. 2006-275713, the entire contents of the patent application, and the entire contents of the Abstract of

Claims (8)

A liquid crystal alignment agent characterized by containing the following polyoxyalkylene (A) and ethylene glycol compound (B), and relative to the total alkoxy decane to be used for obtaining polyoxyalkylene (A) 100 parts by mass of the SiO ₂ atom, the content of the ethylene glycol compound (B) is 2.5 to 19,800 parts by mass, and the polyoxyalkylene (A): contains an alkoxy decane represented by the following formula (1) a polyoxyalkylene obtained by polycondensation of at least one alkoxydecane, R ¹ _n Si(OR ² ) _4-n (1) (R ¹ represents an organic group having 7 to 30 carbon atoms, and R ² represents a carbon atom a hydrocarbon group of 1 to 5, n represents an integer of 1 to 3) an ethylene glycol compound (B) having two carbon atoms bonded to a hydroxyl group and a hydrogen atom, and the two carbon atoms may have a hetero atom An aliphatic group-bonded structure and a continuous ethylene glycol compound having 3 to 6 carbon atoms. The liquid crystal alignment agent of claim 1, which further comprises the solvent (C) which is a solvent having a hydroxyl group and is an ethylene glycol as defined in the first aspect of the patent application. A solvent of a compound having a different structure of the compound (B). The liquid crystal alignment agent according to claim 1 or 2, wherein the polyoxyalkylene (A) contains 0.1 to 30 mol% of the alkoxydecane represented by the formula (1) in the peralkyl alkane. The polyoxyalkylene obtained by polycondensation of the alkoxy decane. The liquid crystal alignment agent of claim 1 or 2, wherein the polyoxyalkylene (A) is used in combination of at least one of the alkoxydecane represented by the formula (1) and at least one of A polyoxyalkylene obtained by polycondensation of an alkoxydecane of an alkoxydecane represented by the formula (2), R ³ _m Si(OR ⁴ ) _4-m (2) (R ³ represents a hydrogen atom, a halogen atom or a carbon atom The organic group of 1 to 6, R ⁴ represents a hydrocarbon group having 1 to 5 carbon atoms, and m represents an integer of 0 to 3). The liquid crystal alignment agent of claim 1 or 2, wherein the ethylene glycol compound (B) is selected from the group consisting of 1,3-propanediol, 1,3-butanediol, and 1,4-butane. Glycol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,6-hexanediol, diethyl At least one or more of a group of a diol and a dipropylene glycol. The liquid crystal alignment agent of claim 1 or 2, wherein the content of the polyoxyalkylene (A) in the liquid crystal alignment agent is a total alkoxy decane used for obtaining the polyoxyalkylene (A). the silicon atom, in terms of SiO ₂ in terms of SiO ₂ concentration of 0.5 to 20% by mass. A liquid crystal alignment film which is obtained by using a liquid crystal alignment agent according to any one of claims 1 to 6. A liquid crystal display element characterized by having a liquid crystal alignment film according to item 7 of the patent application.